Reaction Of Isatins Research Articles

On the Reaction of Isatin with Cyanomethylene(triphenyl)-phosphorane. A Nucleophilic Attack of Alkyl Phosphites on the Carbon–Carbon Double Bond of ( E)-Oxindolylideneacetonitrile

The reaction of cyanomethylene(triphenyl)phosphorane ( 2) with isatin ( 1) in dry benzene at room temperature for 1 h led to the formation of (1,2-dihydro-2-oxo-3H-indol-3-yl)acetonitrile as a mixture of E- and Z-stereo isomers 3 and 4. Trialkyl phosphites 7 reacted with ( E)-nitrile 3 in dry benzene at 70°C for about 10 h to give the phosphonates 8 as two isomers together with the unexpected spiro products of isomers 9. When the ( E)-nitrile 3 was allowed to react with dialkyl phosphites ( 11) without solvents at 100°C for about 30 h, a mixture of the phosphonate derivatives 8 and one isomer of the dimeric structure 9 were obtained. The reaction mechanisms are considered and the structural assignments of the new compounds are based on chemical and spectroscopic evidence.

Spirocyclization of Isatin with Chiral α-Aminothiols: Diastereoselective Synthesis of (-)- and (+)-4'-(Methoxycarbonyl)spiro[indoline-3,2'-thiazolidin]-2-one

Reactions of isatin with chiral α-aminothiols have been studied. With L-cysteine, only decomposition products were formed under various reaction conditions, whereas D- and L-penicillamine afforded mixtures of diastereomeric 4'-carboxy-5',5'-dimethylspiro[indoline- 3,2'-thiazolidin]-2-ones (4a and 4b or 5a and 5b) in the ratio 1 : 1. The reaction of isatin with methyl L- and D-cysteinates under mild reaction conditions (methanol-benzene, room temperature) proceeded diastereoselectively with the formation of (-)- and (+)-4'-(methoxycarbonyl)spiro[indoline-3,2'-thiazolidin]-2-one (6a and 8) in 38 and 30% yields, respectively. Optically inactive 4'-(methoxycarbonyl)spiro[indoline-3,2'-([2',5']dihydrothiazol)]-2-one (7) was isolated as a side product in 7 and 3% yield, respectively. Structure of the obtained products was determined by spectral methods, including NOE difference measurements and by X-ray crystallography.

Preparation of 3,3-Diaryloxindoles by Superacid-Induced Condensations of Isatins and Aromatics with a Combinatorial Approach

3,3-Diaryloxidoles are prepared in high yields (62−99%) by reaction of isatin or substituted isatins with aromatics in triflic acid. The reaction shows a significant dependence on acid strength which suggests the formation of diprotonated, superelectrophilic intermediates. Reaction of isatin, benzene, and acid systems of varying strength (composed of CF3SO3H and CF3CO2H) showed that the acid strength must be more acidic than Ho = −11.5 for complete conversion to product. Reaction of isatins with mixtures of aromatics allows for the preparation of libraries of 3,3-diaryloxindole products by combinatorial synthesis.

The Reaction of Isatin with Alkoxycarbonylmethylene (Triphenyl)Phosphoranes

Isatin (1) reacted with alkoxycarbonylmethylene(triphenyl)phosphoranes (2) in boiling benzene for about 3 h to give orange yellow crystalline products of alkyl (1,2-dihydro-2-oxo-3H-indol-3-yl)acetates (3). The double bond of compounds 3 was reduced with zinc dust in boiling acetic acid to give 5, which upon methylation with methyl iodide in dry acetone and anhydrous potassium carbonate yielded the corresponding products 6. The structural assignments of the new compounds are based on the spectroscopic results.

Synthesis and study of 3-(triphenylphosphoranylidene)-2,3-dihydro-1H-indol-2-one

The reaction of isatin 1 (2,3-dihydroindole-2,3-dione) and triphenylphosphine 2 afforded the new title compound 6 and isoindigo 7 and not the earlier proposed indirubin 3. Wittig reactions of 6 with the benzaldehydes 8a–c gave the corresponding (Z-)- and (E)-3-(arylmethylidene)-2, 3-dihydro-1H-indol-2-ones 9a–c and 10a–c, respectively, in moderate yields.

Structure of the (2-acetamidobenzoyl)formate anion as the benzamidinium salt

The reaction of isatin with benzamidine hydrochloride in methanol yields the title compound, benzamidium (2-acetamidobenzoyl)formate (C 7 H 9 N 2 + . C 10 H 8 NO 4 − ). In the benzamidinium cation the configuration about the exocyclic C atoms is planar, resulting in electron delocalization in the C−N bonds. The C−O bond distances in the carboxylate moeity in the anion are very similar (average C−O = 1.237 A), indicating delocalization of the negative charge. Hydrogen bonds are present between the N atoms of the amidinium group and the 0 atoms of the carboxylate moeity of the anion. The N...O distances vary between 2.819 (5) and 2.901 (5) A in the hydrogen bonds

The Synthesis of Heterocycles from Indolin-2-one Derivatives and Active Methylene Reagents

Investigation the synthesis of multifunctionalized heterocyclic spiro derivatives via the reaction of isatin, ethyl cyanoacetate and an other active methylene compound. It has been found that refluxing of an ethanolic piperidine solution of equimolar ratios of isatin (Ia), ethyl cyanoacetate (II) and barbituric acid (IIIa) or thiobarbituric acid (IIIb) afforded a solid product whose structure was assumed, in accordance with elemental analysis and IR and 1H NMR spectra, to be VIIIa and VIIIb. Confirmation of the structures VIIIa and VIIIb follows from their preparation from compound IV, synthesized separately, and barbituric acids IIIa and IIIb in 1 : 1 molar ratio under the same reaction conditions.

Synthesis and properties of 2-(2-oxoindolin-3-ylidene)-2-cyanoacetic acid piperidides and morpholides

The reaction of isatins with cyanoacetic acid piperidide or morpholide gives the corresponding derivatives of 2-(2-oxoindolin-3-ylidene)-2-cyanoacetic acid, which may be reduced to give amides of 2-(2-oxoindolin-3-yl)-2-cyanoacetic acid and react with ethanolic alkali to give quinoline derivatives.

ChemInform Abstract: X=Y‐ZH Compounds as Potential 1,3‐Dipoles. Part 28. The Iminium Ion Route to Azomethine Ylides. Background and Reaction of Amines with Bifunctional Ketones.

AbstractThe reaction of isatin (I), ninhydrin (VIII), and acenaphthenequinone (XIII) with amines gives rise to stereospecific formation of intermediate azomethine ylides which can be trapped by cycloaddition with the acrylate (II) or the maleimide (IX) leading to products such as (IV) + (V), (VII) (Pca21; Z = 8), (XI) + (XII), (XV).

X=Y-ZH compounds as potential 1,3-Dipoles. Part 28 1,2 the iminium ion route to azomethine ylides. background and reaction of amines with bifunctional ketones.

The reaction of isatin, ninhydrin and acenaphthenequinone with primary and secondary amines gives rise to stereospecific formation of intermediate azomethine ylides which can be trapped by cycloaddition to methyl acrylate or N-methylmaleimide. The regiochemistry of the cycloadditions to methyl acrylate is controlled by both frontier orbital and steric interactions with the latter dominating in the examples studied.

ChemInform Abstract: Synthesis of Quinoline‐4‐carboxylic Acid and Its Derivatives.

2-Methylquinoline-4-carboxylic acid was obtained by the reaction of isatin with acetone in the presence of an alkali. This acid was converted through a step involving (E)-2-styrylquinoline-4-carboxylic acid to quinoline-2,4-dicarboxylic acid, from which quinoline-4-carboxylic acid was obtained by refluxing in nitrobenzene. The structures of the synthesized compounds were confirmed by 1H NMR spectroscopy using two-dimensional (2DJ) spectra.

Synthesis of quinoline-4-carboxylic acid and its derivatives

2-Methylquinoline-4-carboxylic acid was obtained by the reaction of isatin with acetone in the presence of an alkali. This acid was converted through a step involving (E)-2-styrylquinoline-4-carboxylic acid to quinoline-2,4-dicarboxylic acid, from which quinoline-4-carboxylic acid was obtained by refluxing in nitrobenzene. The structures of the synthesized compounds were confirmed by 1H NMR spectroscopy using two-dimensional (2DJ) spectra.

Reaction of isatin with bromo ketones under interphase-catalysis conditions

Reaction of isatin with bromo ketones under interphase-catalysis conditions

Side-bonded ketone complexes of platinum(0). Alloxan and diethyl oxomalonate complexes and reactions of platinum(0) complexes with isatin and benzoyl cyanide.

Reactions of alloxan (all) with [PtL(PPh 3) 2] (L′= trans -stilbene, L″ diphenylacetylene) afford the side-bonded ketone complex [Pt(all)(PPh 3) 2] which may also be obtained from the hydrate of alloxan and [PtL′(Pph 3) 2]. Similarly diethyl oxomalonate (dio) and [Pt(PPh 3) 4] afford a side-bonded ketone complex [Pt(dio)(PPh 3) 2]. Reaction of isatin with [Pt(PPh 3 4] gives trans -[PtH{ NCO( o-C 6H 4)CO }(PPh 3) 2] and benzoyl cyanide and [PtL′(PPh 3) 2] give cis -[Pt(CN)(COPh 3) 2] and trans -[Pt(CN) 2(PPh 2) 2].

Structures of isamic acid and methylisatoid

Isamic acid, a red crystalline product from the reaction of isatin with ammonia, is proved to be 1,2-dihydro-2-oxospiro-[3H-indole-3,2′(1′H)-quinazoline]-4′-carboxylic acid, as suggested by G. F. Field. The colour and lack of basicity appear to be due in part to spiroconjugation. Methylisatoid, from O-methylisatin and moist air or aqueous acetic acid, is shown by rational synthesis and degradation to be methyl 6,12-dihydro-12-hydroxy-6-oxoindolo-[2,1-b]quinazoline-12-carboxylate.

ChemInform Abstract: THE CHEMISTRY OF ISATIN

Publisher Summary This chapter reviews developments in the field of isatin from 1944 to late 1974. The most frequently used synthesis of isatins is the Sandmeyer procedure, which involves the formation of an isonitrosoacetanilide from an aniline, chloral hydrate, and hydroxylamine. The isonitrosoacetanilide is converted into the isatin on treatment with sulfuric acid, or less frequently polyphosphoric. The Sandmeyer method has been used with di- and trisubstituted aniline to prepare di- and tri-substituted isatins. Isatin sodium or potassium salts react with dimethyl and dieth sulfate, a variety of alkyl halides, acyl halides, and anhydrides to give N-alkyl and N-acylisatins. N-substitutcd isatins have also been prepared by reactions of some of the compounds that were described earlier. A number of reactions that do not reasonably fit in other categories are included in this chapter. A number of complexes of isatin and metal salts have been reported. Extensive studies have been reported on infrared vibrational frequency correlations of isatin and a variety of substituted isatin. A number of studies of the ultraviolet absorption spectra of isatins have appeared. The most frequently reported oxidation reaction of isatins is the oxidation with alkaline hydrogen peroxide to give anthranilic acids. This procedure has been both as a proof of structure of isatins and as a method of synthesis of anthranilic acids. A wide variety of substituted isatins has reacted with hydroxylamine to give isatin-3-oximes. The cyclizations of certain 2-substituted isatin derivatives were studied so as to compare them with the above cyclizations. The chapter closes with a discussion on polymers.

The reaction of isatin with an excess of ethylamine

The reaction of isatin with an excess of ethylamine

The reaction of isatin with cycloalkylamines

The reaction of isatin with cycloalkylamines

Synthesis of amino derivatives of quinoline and 5, 6-benzoquinoline

3-Aminocinchophen and 2-phenyl-3-aminoquinolines were synthesized by the reaction of isatin and 5-, 6-, and 7-methylisatins with ω-aminoacetophenone in alkaline media. A number of 3-amino-5,6-benzoquinoline derivatives were obtained by the condensation of azomethines from aromatic aldehydes and β-naphthylamine with ω-aminoacetophenone.

Analogs of atophan containing a furan nucleus

By the reaction of isatin and 5-, 6-, and 7-methylisatins with 2-acetylfuran and 2-acetylbenzofuran in an alkaline medium new analogs of atophan have been synthesized. The compounds obtained are physiologically active substances and plant growth stimulators.